Sorption of organic compounds by pyrolyzed humic acids

Humic acids (HAs) are frequently subjected to pyrolysis and carbonization by wildfires, which could significantly change the sorption of organic contaminants and their environmental risks in natural system. In previous studies, sorption of organic compounds was investigated for HAs pyrolyzed at temperature below 330 °C, but not for HAs pyrolyzed at higher temperature. Therefore, in this study, sorption of 22 typical organic compounds by HAs pyrolyzed at a series of temperatures from 300 to 700 °C was investigated. Sorption of organic compounds was dominated by nonlinear partition for HAs pyrolyzed at low temperature (e.g., 300 and 400 °C) due to the aliphatic and nonporous structures of pyrolyzed humic acids (PyHAs), while it was dominated by pore-filling adsorption for HAs pyrolyzed at high temperature (e.g., 700 °C) due to the aromatic and porous structures of PyHAs. For HAs pyrolyzed at moderate temperature (e.g., 450, 500 and 600 °C), both nonlinear partition and pore-filling adsorption were responsible for the sorption of organic compounds. Meanwhile, the contribution of pore-filling adsorption to overall sorption increased but the contribution of nonlinear partition decreased with the increasing pyrolytic temperature of PyHAs, attributed to the structure change of PyHAs from aliphatic and nonporous to the aromatic and porous. Moreover, with the increasing pyrolytic temperature of PyHAs, sorption affinity of organic compounds increased, while the change of sorption capacity could be explained by the decrease of nonlinear partition and the increase of pore-filling adsorption. The obtained results could help to evaluate the transport, bioavailability and health risks of organic contaminants in the environment.